T-matrix representation and long time behavior of observables in the theory of migration-influenced irreversible reactions in liquid solutions

The theory of migration-influenced irreversible reactions upon binary encounters of reactants in liquid solutions is formulated in terms similar to those of quantum scattering theory. Free motion of a reacting pair in the configuration space is a random walk in three-dimensional infinite space and arbitrary Markovian motion over internal degrees of freedom. In the case of mixing by free motion, general asymptotic properties of the free resolvent describing this motion have been established. General long-time kinetic law of the attainment of steady-state values by the observables in bulk and geminate reactions has been deduced. Thermodynamically, not only the universality of their long-time dependence is important, but also the fact that the rate of attaining the steady-state values is completely determined by macroscopic quasi-equilibrium observables.